Detergent composition

ABSTRACT

The present invention provides a detergent composition containing an N,N-bis(carboxymethyl)glutamic acid salt as an organic builder and being more excellent in detergency than otherwise. The detergent composition comprises (a) an anionic surfactant, (b) a salt of a polymer comprising carboxylic acid units and having a specific molecular weight, (c) an N,N-bis(carboxymethyl)glutamic acid salt represented by the following formula (I), and (d) a crystalline aluminosilicate at specific proportions: ##STR1## wherein M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium or a basic amino group, provided that a plurality of M&#39;s may be the same as or different from each other.

This application is the national phase under 35 U.S.C. §371 of prior PCTInternational Application No. PCT/JP97/03528 which has an Internationalfiling date of Oct. 2, 1997 which designated the United States ofAmerica, the entire contents of which are hereby incorporated byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a detergent composition. In particular,it relates to a detergent composition which contains a water-solubleamino polycarboxylic acid compound excellent in biodegradability andexhibits excellent detergency.

2. Description of Related Art

A detergent for clothes is composed of a surfactant which solubilizessoil, separates it from fibers, and dissolves or disperses it in a waterfor washing, an alkali agent which accelerates the decomposition orsolubilization of soil, a polymeric substance which suspends soil, asequestering agent which removes substances lowering the power ofsurfactants, for example, calcium, magnesium and so on from a water forwashing, and so on.

Among these components, the substance, called a builder in general, doesnot exhibit detergency by itself, but can enhance the detergency of asurfactant used together. In the builder for a detergent, theabove-mentioned sequestering agent serves to make a surfactant exhibitits performance more effectively, thus being one of extremely importantbuilders.

Phosphorus compounds such as sodium tripolyphosphate were formerly addedto a detergent for clothes as the builder (i.e., sequestering agent).However, phosphorus compounds were believed to be one of the factorscausing the eutrophication of rivers, lakes, ponds and so on. In thedetergent industry, therefore, the use of phosphate builders wasself-restrained, while the development of a detergent without anyphosphate builder had been continued. As a result, a zeolite, acrystalline sodium aluminosilicate, having a specific structure was usedas the main component of the sequestering agent.

Although the zeolite was used as the main builder substitute forphosphorus compounds, it had some problems that the performance thereofin low-temperature washing in a short time was often unsatisfactory andthat the degree of freedom of the formulation was restricted in order todecrease the quantity of insolubles derived from zeolite which wasessentially insoluble in water.

Owing to the recent high concern about the influence on the environment,studies have been made on organic builders excellent in biodegradabilityand sequestering performance. There is so this background that, forexample, a specific organic builder prepared by the reaction ofepoxysuccinic acid or maleic acid with aspartic acid and a detergentcomposition containing it is disclosed in JP-A 5-170714, and a detergentcomposition containing a builder consisting of hydroxyiminodisuccinicacid in a specific amount is disclosed in JP-A 6-248300.

Further, it is suggested in JP-A 50-3979 and JP-A 56-81399 that anN,N-bis(carboxymethyl)glutamic acid salt is superior to the aboveorganic builders in calcium sequestering performance andbiodegradability, and such a salt is usable as builders for a detergent.However, these patent documents are silent on the detergent compositionwhich enable the builders to exhibit their effects sufficiently.

DISCLOSURE OF THE INVENTION Summary of the Invention

An object of the present invention is to find the optimum formulationbringing about higher detergency with respect to a detergent compositionprepared by adding an N,N-bis(carboxymethyl)glutamic acid salt, which isa biodegradable water-soluble chelating agent, to a compositioncomprising both an anionic surfactant as the base and a zeolite which isan inorganic builder.

The inventors of the present invention have intensively studied to findthat the above problems can be solved by a detergent compositionprepared by adding an N,N-bis(carboxymethyl)glutamic acid salt and acarboxylated polymer respectively in specific proportions to acomposition comprising both an anionic surfactant and a zeolite. Thepresent invention has been accomplished on the basis of this finding.

Namely, the present invention provides a detergent compositioncomprising

(a) 15 to 50% by weight of an anionic surfactant,

(b) a polymer comprising units derived from at least one member selectedfrom the group consisting of monoethylenically unsaturatedmonocarboxylic acids and monoethylenically unsaturated dicarboxylicacids and having a weight-average molecular weight of 1,000 to 150,000,or a salt of the polymer,

(c) an N,N-bis(carboxymethyl)glutamic acid salt represented by thefollowing formula (I): ##STR2## wherein M is a hydrogen atom, an alkalimetal, an alkaline earth metal, an ammonium or a basic amino group,provided that a plurality of M's may be the same as or different fromeach other, and

(d) 5 to 40% by weight of a crystalline aluminosilicate,

the total amount of the components (b) and (c) being 1 to 20% by weightbased on the composition, the weight ratio of the component (b) to thecomponent (c) ranging from 1/10 to 10/1.

In the present invention, an anionic surfactant is used as the component(a) in an amount of 15 to 50% by weight, preferably 25 to 45% by weight.The use thereof in such an amount brings about satisfactory detergencyand facilitates the preparation of the detergent composition. Theanionic surfactant usable in the present invention is one or moresurfactants selected from the group consisting of alkylbenzenesulfonateshaving 8 to 16 carbon atoms, alkanesulfonates (SAS), α-olefinsulfonates,sulfates of primary or secondary higher (fatty) alcohols and α-sulfofatty acid salts.

The polymer or salt thereof as the component (b) is one comprising unitsderived from at least one member selected from the group consisting ofmonoethylenically unsaturated monocarboxylic acids and monoethylenicallyunsaturated dicarboxylic acids and having a weight-average molecularweight of 1,000 to 150,000, preferably 10,000 to 100,000, desirably a(co)polymer comprising repeating units represented by the followingformula (IV) or a salt of the polymer. The salt of the copolymer may beany of partially and wholly neutralized ones. ##STR3## wherein M is acounter ion and a copolymerizing ratio of x/y ranges from 0/10 to 5/5 asa mole ratio.

This copolymer salt is a sodium or potassium salt of a homo- orcopolymer prepared by polymerizing maleic acid (i) with acrylic acid(ii) at a (i) to (ii) mole ratio of 0/10 to 5/5, preferably 2/8 to 5/5,and having a weight-average molecular weight of 1,000 to 150,000,preferably 10,000 to 100,000. When the (i) to (ii) mole ratio or themolecular weight deviates from the above range, the composition willshow no satisfactory detergency.

In the present invention, an N,N-bis(carboxymethyl)glutamic acid saltrepresented by the following formula (I) is used as the component (c):##STR4## wherein M is a hydrogen atom, an alkali metal, an alkalineearth metal, an ammonium or a basic amino group, provided that aplurality of M's may be the same as or different from each other.

In the present invention, excellent detergency can be attained by addingthe N,N-bis(carboxymethyl)glutamic acid salt (c) in a total amount ofthe components (b) and (c) of 1 to 20% by weight, preferably 1 to 10% byweight based on the composition and at a (b) to (c) weight ratio of 1/10to 10/1, preferably 3/10 to 10/3, still preferably 3/7 to 7/3. When the(b) to (c) weight ratio deviates from this range, the composition willshow no satisfactory detergency.

A crystalline aluminosilicate is used as the component (d), which isgenerally called "zeolite" and represented by the following formula (i),preferably by the following formula (ii):

    a'(M.sub.2 O)·Al.sub.2 O.sub.3 ·b'(SiO.sub.2)·w(H.sub.2 O)             (i)

wherein M is an alkali metal; and a', b' and w represent molar ratios ofthe components and, in general, 0.7≦a'≦1.5, 0.8≦b'<6, and w is anarbitrary positive number,

    Na.sub.2 O·Al.sub.2 O.sub.3 ·n(SiO.sub.2)·w(H.sub.2 O)              (ii)

wherein n is a number of 1.8 to 3.0; and w is a number of 1 to 6.

The crystalline aluminosilicate (zeolite) to be used is desirably asynthetic zeolite having an average primary particle diameter of 0.1 to10 μm, for example, zeolite A, X or P. The zeolite may be added in theform of a powder and/or a dry agglomerate prepared by drying a zeoliteslurry. In the present invention, such a crystalline aluminosilicate isadded in an amount of 5 to 40% by weight, preferably 10 to 35% by weightbased on the composition. When the amount of the crystallinealminosilicate used lies in this range, the composition will show anexcellent detergency.

DETAILED DESCRIPTION OF THE INVENTION

The detergent composition of the present invention may further containoptional components which will now be described, in addition to theabove essential components (a), (b), (c) and (d).

The nonionic surfactant to be optionally used includes C₈ -C₂₂polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, higherfatty acid alkanolamides and adducts thereof with alkylene oxides,sucrose fatty acid esters, alkyl and alkenyl glucosides, glycerol fattyacid monoesters and adducts thereof with alkylene oxides, and alkylamineoxides. The amphoteric surfactant to be optionally used includes aminoacid base surfactants and N-acylamino acid base ones, while the cationicsurfactant to be optionally used includes quaternary ammonium salts.Further, conventional builders for detergent may optionally be used, andspecific examples thereof include carbonate salts such as soda ash,sulfate salts, sulfite salts, silicates, crystalline silicates,polyglyoxylic acid salts described in JP-A 54-52196, citric acid,oxydisuccinic acid, and nitrilotriacetic acid salts.

In particular, it is preferable that the detergent composition of thepresent invention contains a crystalline silicate. The term "crystallinesilicate" used in this invention is such that a 0.1% dispersion liquidthereof may have the maximum pH of 11 or above (at 25° C.) and inparticular 5 ml or more of a 0.1N aqueous solution of HCl may benecessary to decrease the pH of one liter of a 0.1% dispersion liquid ofthe crystalline silicate to pH 10 and it may be excellent in not onlyalkalinity but also alkali buffer capacity. In the present invention,alkali metal salts of silicic acid (SiO₂) are preferably used, amongwhich alkali metal silicates having a SiO₂ to M₂ O ratio of 0.5 to 2.6(wherein M is an alkali metal) are still preferable. Although the SiO₂to Na₂ O ratios of known crystalline silicates lie within the range of1.9 to 4.0, crystalline silicates having SiO₂ to Na₂ O ratios exceeding2.6 are often unsuitable for high-density detergents.

Examples of the crystalline silicates to be favorably used in thepresent invention include those having the following compositions:

    1x(M.sub.2 O)·y(SiO.sub.2)·z(Me.sub.m O.sub.n)·w(H.sub.2 O)                            (II)

wherein M is a Group Ia element of the periodic table; Me is one elementselected from the group consisting of Group IIa, IIb, IIIa, IVa and VIIIelements of the periodic table or a combination of two or more elementsselected therefrom; y/x is 0.5 to 2.6; z/x is 0.01 to 0.9; w is 0 to 20;and n/m is 0.5 to 2.0, and

    2M.sub.2 O·x'(SiO.sub.2)·y'(H.sub.2 O)   (III)

wherein M is an alkali metal; x' is 1.5 to 2.6; and y' is 0 to 20.

First, the crystalline silicates 1 represented by the above formula (II)will be described.

In the formula (II), M is selected from among Group Ia elements of theperiodic table, and such elements include Na, K and so on. The M₂ Ocomponent may be constituted of an oxide of one of the elements, oralternatively, it may be constituted of oxides of two or more of them,for example, a mixture of Na₂ O with K₂ O.

Me is selected from the group consisting of the Group IIa, IIb, IIIa,IVa and VIII elements of the periodic table, and examples of suchelements include Mg, Ca, Zn, Y, Ti, Zr and Fe. Among them, Mg and Ca arepreferable from the standpoints of resources and safety, though Me isnot particularly limited. The Me_(m) O_(n) component may be constitutedof an oxide of one of the elements, or alternatively it may beconstituted of oxides of two or more of them, for example, a mixture ofMgO with CaO.

In the formula (II), y/x is 0.5 to 2.6, preferably 1.5 to 2.2. When y/xis less than 0.5, the resulting silicate will be poor in resistance todissolution in water (water resistance), which will exert remarkableadverse effects on the physical properties of the detergent compositionas powder, for example, caking properties and solubility . On thecontrary, when y/x exceeds 2.6, the resulting silicate will beunsatisfactory as alkali agent owing to its low alkalinity and as ionexchanger owing to its poor ion-exchange capacity. In the formula (II),z/x is 0.01 to 0.9, preferably 0.02 to 0.9, still preferably 0.02 to0.5. When z/x is less than 0.01, the resulting silicate will be poor inwater resistance, while when z/x exceeds 1.0, the resulting silicatewill be poor in ion exchange capacity to result in an unsatisfactory ionexchanger. No particular limitation is placed on x, y and z, so far asx, y and z satisfy the relationships represented by the y/x and z/x.When the x(M₂ O) component is x'(Na₂ O)·x"(K₂ O) as described above, xis x' plus x'. Such a relationship applies also to z, when the z(Me_(m)O_(n)) component is composed of two or more members. Further, n/m meansthe number of oxide ions coordinating to the element Me, which isselected substantially from the group consisting of 0.5, 1.0, 1.5 and2.0.

The crystalline silicate represented by the formula (II) is composed ofthree components, i.e., M₂ O, SiO₂ and Me_(m) O_(n). Therefore, rawmaterials for the three components are necessary in preparing thecrystalline silicate represented by the formula (II). The raw materialsare not particularly limited, but may suitably be selected from amongknown compounds. For example, the raw material for the M₂ O or Me_(m)O_(n) component includes oxides, composite oxides, hydroxides and saltsof the elements and minerals containing the elements. Specifically, theraw material for the M₂ O component includes NaOH, KOH, Na₂ CO₃, K₂ CO₃,Na₂ SO₄ and so on, while that for the Me_(m) O_(n) component includesCaCO₃, MgCO₃, Ca(OH)₂, Mg(OH)₂, MgO, ZrO₂, dolomite and so on. The rawmaterial for the SiO₂ component includes silica rock, kaolin, talc,fused silica, sodium silicate and so on.

The crystalline silicate represented by the formula (II) can be producedby, for example, a process which comprises mixing the above rawmaterials at such a predetermined ratio as to give the x, y and z valuesof the objective crystalline silicate, and firing the obtained mixturegenerally at 300 to 1500° C. preferably at 500 to 1000° C., stillpreferably at 600 to 900° C. to conduct crystallization. When the firingis conducted at a temperature lower than 300° C., the resulting silicatewill be poor in water resistance owing to its low crystallinity, whilewhen it is conducted at a temperature exceeding 1500° C., course grainswill be formed to result in a poor ion exchange capacity. The heatingtime is generally 0.1 to 24 hours. The firing may be conducted by theuse of an electric or gas furnace or other heating furnaces.

The produced crystalline silicate represented by the formula (II)exhibits a pH of 11 or above in the form of a 0.1% by weight aqueousdispersion thereof, thus being excellent in alkalinity. Further, it isparticularly excellent in alkali buffer effect and the effect is moreexcellent than that of sodium carbonate or potassium carbonate.

The crystalline silicate has an ion exchange capacity of at least 100CaCO₃ mg/g, preferably 200 to 600 CaCO₃ mg/g, and is one of thesubstances having sequestering power according to the present invention.

As described above, the crystalline silicate represented by the formula(II) has both high alkalinity and alkali buffer effect and exhibits ahigh ion-exchange capacity, so that the use thereof in a suitablyselected amount permits the employment of favorable washing conditions.

It is preferable that the crystalline silicate represented by theformula (II) have an average particle diameter of 0.1 to 100 μm, stillpreferably 1 to 60 μm. When the average particle diameter exceeds 100μm, the development of ion exchange of the silicate will be so slow asto bring about a lowering in the detergency, while when it is less than0.1 μm, the resulting silicate will exhibit high absorptivity formoisture and CO₂ owing to its enhanced specific surface area to resultin remarkably deteriorated quality. The term "average particle diameter"used in this invention refers to a median diameter of particle sizedistribution.

The crystalline silicate having the above average particle diameter andparticle size distribution can be produced through pulverization by theuse of a vibration mill, a hammer mill, a bowl mill, a roller mill orother pulverizers.

Then, the crystalline silicate 2 represented by the formula (III) willbe described.

The crystalline silicate 2 is one represented by the formula (III):

    M.sub.2 O·x'(SiO.sub.2)·y'(H.sub.2 O)    (III)

wherein M is an alkali metal; x' is 1.5 to 2.6; and y' is 0 to 20. Inparticular, those represented by the formula (III) wherein 1.7≦x'≦2.2and y'=0 are preferable and those having a cation exchange capacity of100 to 400 CaCO₃ mg/g are usable. The crystalline silicate representedby the formula (III) is one of the substances having a sequesteringpower according to the present invention.

As described above, the crystalline silicate represented by the formula(III) has both high alkalinity and alkali buffer effect and exhibits ahigh ion-exchange capacity, so that the use thereof in a suitablyselected amount permits the employment of favorable washing conditions.

The crystalline silicate represented by the formula (III) is generallyprepared by firing amorphous glassy sodium silicate at 200 to 1000° C.to crystallize it, though the production of which is described in JP-A60-227895. Details of the production are described in, for example,Phys. Chem. Glasses. 7, 127-138 (1966), Z. Kristallogr., 129, 396-404(1969) and so on. Further, the crystalline silicate represented by theformula (III) is commercially available under the trade name of"Na-SKS-6" (δ-Na₂ Si₂ O₅) from Hoechst Tokuyama Ltd. as powder orgranule.

It is preferable that the crystalline silicate represented by theformula (III) as well as the one represented by the formula (II) have anaverage particle diameter of 0.1 to 100 μm, still preferably 1 to 60 μm.

In the present invention, the crystalline silicates represented by theformula (II) and those represented by the formula (III) may be used eachalone or as a mixture of two or more of them. Further, it is preferablethat the silicates account for 30 to 100% by weight, still preferably 70to 100% by weight of the alkali agent contained in the composition.

In the present-invention, the crystalline silicate is added in an amountof 1 to 40% by weight, preferably 5 to 35% by weight based on thecomposition. When the amount is too small, the resulting compositionwill be poor in detergency, while when it exceeds 40% by weight, theresulting composition will cause caking or lowering in the physicalproperties as powder owing to its enhanced adsorptivity for moisture,resulting in a difficult handling.

Further, the detergent composition of the present invention may containan enzyme such as protease, cellulase, amylase or lipase. Furthermore,it may contain other minor components, and examples of such minorcomponents include conventional perfumes (such as ones described in JP-A63-101496); foam inhibitors such as silica and silicone; fluorescentbrightening agents such as biphenyl-base ones, stilbene-base ones andcombinations of both; and anticaking agents such as p-toluenesulfonicacid salts, xylenesulfonic acid salts, acetic acid salts, sulfosuccinicacid salts, talc, finely powdered silica, and clay. Among finelypowdered silica and so on, porous one is usable as a carrier fornonionic surfactants. Clay (i.e., smectite clay) is effective also assoftener.

The detergent composition of the present invention may further contain ableach composition such as sodium percarbonate or sodium perborate, withsodium percarbonate being particularly preferable.

The detergent composition of the present invention can take any formselected from the group consisting of liquid, powder and granule, and itcan be produced by conventional known processes, for example, spraydrying, spray mixing, granulation by pulverization, impregnation withbeads containing inorganic builders, processes for producinghigh-density granular detergents, processes for producing tabletted,flaky or rodlike detergents, or processes for producing liquiddetergents by batch or continuous blending.

The process for the production of a powdered or granular detergentcomposition according to the present invention is not particularlylimited, but known processes can be employed for the production.Further, the powdered or granular detergent composition may be onehaving a high bulk density. The bulk density of the composition can beincreased by, for example, a method of spraying a nonionic surfactant onspray-dried particles, a method of making a powdery component containingan oil-absorbing carrier occlude a nonionic surfactant directly. It isoptional to refer to disclosures of JP-A 61-69897, 61-69899, 61-69900,2-222498, 2-222499, 3-33199, 5-86400 and 5-209200. A small portion ofthe aluminosilicate may be added during the granulation or just beforethe completion thereof for the purpose of modifying the surfaces of thegranules. When a crystalline silicate is used, it is preferable that thesilicate be added in the step of enhancing the bulk density or by dryblending. When an alkali metal carbonate is used, it may be added intothe slurry, during the granulation, or by dry blending.

When the detergent composition has a powdery or granular form, it isdesirable from the standpoint of the physical properties of thecomposition as powder that the average particle diameter is 200 to 1000μm, particularly desirably 200 to 600 μm. In this case, the bulk densityis about 0.5 to 1.2 g/cm³, preferably about 0.6 to 1.0 g/cm³.

The detergent composition of the present invention may be used in asuitable concentration, which depends on the methods of washing, such asmachine washing or immersion, the quantity of clothes or water, thedegree of stains, the operating conditions of the machine, or the like.In machine washing, for example, the composition may be used in aconcentration of 0.03 to 0.3% by weight.

EXAMPLES

The present invention will now be described in detail by referring tothe following Examples, though the present invention is not limited bythem.

Synthesis Example 1 Synthesis of tetrasodiumN,N-bis(carboxymethyl)glutamate

A reactor was charged with 314.0 g of L-glutamic acid, 350.0 g of a 40%aqueous solution of sodium hydroxide and 200.0 g of water. Thetemperature of the contents was raised to 90° C., followed by theaddition of 110.6 g of prussic acid, 405.4 g of 30% formalin and 450.0 gof a 40% aqueous solution of sodium hydroxide. The resulting mixture wasstirred at 105° C. for 2 hours. After the completion of the reaction,the residual prussic acid was decomposed by the addition of 30.0 g of10% formalin. 1000.0 g of a 40% aqueous solution of sulfuric acid wasadded to the resulting mixture to conduct crystallization. Thecrystalline product thus deposited was recovered by filtration to obtain441.8 g of N,N-bis(carboxymethyl)glutamic acid as a crude crystal. Thiscrude crystal was recrystallized from water/methanol to give 411.9 g ofpurified N,N-bis(carboxymethyl)glutamic acid (yield: 75.5%). This acidwas neutralized with 40% aqueous sodium hydroxide to give a tetrasodiumN,N-bis(carboxymethyl)-glutamate.

Synthesis Example 2 Preparation of Crystalline Silicate (2)

Sodium hydroxide (55.9 parts by weight) and potassium hydroxide (8.5parts by weight) were added to No. 2 sodium silicate (SiO₂ /Na₂ O: 2.5)(1000 parts by weight). The obtained mixture was agitated in a homomixerto dissolve the sodium hydroxide and potassium hydroxide. Finely dividedanhydrous calcium carbonate (5.23 parts by weight) and magnesium nitratehexahydrate (0.13 part by weight) were added to the resulting mixture.The obtained mixture was agitated in a homomixer. A suitable amount ofthe resulting mixture was transferred to a nickel-made pot, fired at700° C. in the air for one hour, rapidly cooled, and pulverized to givea crystalline silicate (2) according to the present invention. Thispowder exhibited a cation exchange capacity (CEC) of as high as 305CaCO₃ mg/g. The average particle diameter of the silicate (2) thusobtained was 22 μm, and a 0.1% dispersion thereof exhibited a pH of 11or above (at 25° C.). The structure and CEC of this crystalline silicate(2) are as follows:

    M.sub.2 O·1.8SiO.sub.2 ·0.02M'O

wherein M is Na and K, the K/Na being 0.03; and M' is Ca and Mg, theMg/Ca being 0.01; average particle diameter: 30 μm; cation exchangecapacity (CEC): 305 CaCO₃ mg/g.

Example 1 Preparation of Detergent Compositions

A detergent composition according to the present invention (Invention 1)was prepared according to the formulation specified in Table 1 by thefollowing process.

An aqueous slurry having a solid content of 50% was prepared by usingLSA, AS, nonion, sodium salt of tallow fatty acid, JIS No. 2 sodiumsilicate, sodium carbonate, potassium carbonate, sodium sulfate,polyethylene glycol, a portion of zeolite (10% of which had beenremoved), tetrasodium N,N-bis(carboxymethyl)glutamate, polyacrylic acidand a fluorescent dye. This slurry was spray-dried into particles,pulverized, and granulated in a high-speed mixer, followed by theaddition of an enzyme and the rest of zeolite as surface modifier andthe spraying with a perfume component. Thus, a final detergentcomposition having a bulk density of 0.8±0.1 g/cm³ was obtained.

Other detergent compositions according to the present invention andcomparative ones were prepared according to the formulations specifiedin Tables 1 and 2 in a similar manner to that described above, whereinthe acrylic acid-maleic acid copolymer was added to each slurry, and thecrystalline silicate (1) was added in the granulation step.

Performance evaluation

The detergent compositions prepared above were each evaluated fordetergency against sebum dirt and mud dirt by the following methods. Theresults are given in Tables 1 and 2.

(1) Test on detergency against sebum dirt (Preparation of artificiallystained cloths)

Artificially stained cloths were prepared by attaching an artificialdirt liquid to cloths. The formulation of the artificial dirt liquidwill be described below. The attachment was conducted by applying theartificial dirt liquid on cloths by the use of a gravure roll coater.The preparation of artificially stained cloths was conducted under theconditions of a cell capacity of gravure roll of 58 cm³ /cm², a coatingspeed of 1.0 m/min, a drying temperature of 100° C., and a drying timeof one minute. Cotton shirting cloth #2003 (a product of Yato Shoten)was used in the above preparation of artificially stained cloths.

Formulation of artificial dirt

    ______________________________________                                        lauric acid      0.44% by weight                                              myristic acid    3.09% by weight                                              pentadecanoic acid                                                                             2.31% by weight                                              palmitic acid    6.18% by weight                                              heptadecanoic acid                                                                             0.44% by weight                                              stearic acid     1.57% by weight                                              oleic acid       7.75% by weight                                              trioleic acid    13.06% by weight                                             n-hexadecyl palmitate                                                                          2.18% by weight                                              squalene         6.53% by weight                                              crystal of egg white lecithin                                                                  1.94% by weight                                              Kanuma Aka-tsuchi                                                                              8.11% by weight                                              carbon black     0.01% by weight                                              tap water        the balance                                                  ______________________________________                                    

(Washing conditions and evaluation method)

Five artificially stained cloths (10 cm×10 cm) prepared above and 1 l ofan aqueous solution of a sample detergent composition were put in aTerg-O-Tometer to conduct washing at 100 rpm. The washing conditions areas follows:

    ______________________________________                                        washing time:      10 min                                                     detergent concentration:                                                                         0.067%                                                     hardness of water: 4° DH                                               temperature of water:                                                                            20° C.                                              rinsing:           with tap water for 5 min                                   ______________________________________                                    

The detergency of each detergent composition was determined by measuringthe reflectivities at 550 nm of the unstained cloth and the stainedcloths before and after the washing by the use of a self-colorimeter(mfd. by Shimadzu Corporation) and calculating the rate (%) of cleansingaccording to the following formula, and the average rate of cleansing offive cloths is given as the detergency of the composition:

Rate of cleansing (%)=(reflectivity after washing-that beforewashing)/(that of unstained cloth-that before washing)×100

(2) Test on detergency against mud dirt

Muddy cloths were prepared by the following process and the detergencyof each detergent composition against the muddy cloths was determined ina similar manner to that employed in the above test. *Preparation ofmuddy cloths (artificially stained cloths)

Kanuma Akadama-tsuchi for horticultural use was dried at 120° C.±5° C.for 4 hours, pulverized and filtered through a 150-mesh screen (openingsize: 100 μm). The undersize portion was dried at 120° C.±5° C. for 2hours and about 150 g thereof was dispersed in one liter of Perclene.Cotton shirting cloth #2023 was brought into contact with the resultingdispersion, followed by brushing. The dispersion was removed, andexcessive dirt attached to the cloth was detached to prepare muddycloth.

Example 2

Detergent compositions according to the present invention (Inventions10, 11, 12 and 13) were prepared respectively in the same manner as thatemployed in preparing the detergent compositions (Inventions 2 to 5)except that the crystalline silicate (2) prepared in Synthesis Example 2was used instead of the crystalline silicate (1) in the same amount asthat used therein. They were subjected to the same detergency test asthat of Example 1. They exhibited excellent detergency.

                                      TABLE 1                                     __________________________________________________________________________                       Invention                                                                     1  2  3  4  5  6                                           __________________________________________________________________________    Formu-                                                                            LAS*.sup.1     25 25 25 25 25 25                                          lation                                                                            AS*.sup.2      10 10 10 10 10 10                                          (wt.                                                                              nonion*.sup.3  2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                         %)  sodium salt of tallow fatty acid                                                             2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                             JIS No. 2 sodium silicate                                                                    5  5  5  5  5  5                                               sodium carbonate                                                                             10 10 10 10 10 10                                              potassium carbonate                                                                          5  5  5  5  5  5                                               sodium sulfate 4.8                                                                              4.8                                                                              4.8                                                                              4.8                                                                              4.8                                                                              4.8                                             PEG*.sup.4     1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                                             cryst. silicate (1)*.sup.5                                                    cryst. sodium aluminosilicate                                                                20 20 20 15 15 15                                              (zeolite 4A)                                                                  tetrasodium    2.5                                                                              2.5                                                                              3.5                                                                              7  3  5                                               N,N-bis(carboxymethyl)-                                                       glutamate                                                                     polyacrylic acid                                                                             2.5                                                            (Mw = 8,000)                                                                  acrylic acid-maleic acid copolymer                                                              2.5                                                                              1.5                                                                              3  7  5                                               (Mw = 50,000)                                                                 enzyme*.sup.6  1.8                                                                              1.8                                                                              1.8                                                                              1.8                                                                              1.8                                                                              1.8                                             fluorescent dye*.sup.7                                                                       0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                             perfume        0.4                                                                              0.4                                                                              0.4                                                                              0.4                                                                              0.4                                                                              0.4                                             water          6  6  6  6  6  6                                           detergency against sebum dirt (%)                                                                63.0                                                                             65.1                                                                             64.5                                                                             67.3                                                                             67.9                                                                             68.1                                        detergency against mud dirt (%)                                                                  60.2                                                                             59.6                                                                             58.7                                                                             60.9                                                                             61.8                                                                             61.8                                        __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________                       Invention                                                                              Comp.                                                                7  8  9  1  2  3  4                                        __________________________________________________________________________    Formu-                                                                            LAS*.sup.1     22.5                                                                             20 20 25 25 25 25                                       lation                                                                            AS*.sup.2      10 10 7.5                                                                              10 10 10 10                                       (wt.                                                                              nonion*.sup.3  2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                      %)  sodium salt of tallow fatty acid                                                             2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                                                              2.5                                          JIS No. 2 sodium silicate                                                                    5  5  5  5  5  5  5                                            sodium carbonate                                                                             10 10 10 10 10 10 10                                           potassium carbonate                                                                          5  5  5  5  5  5  5                                            sodium sulfate 4.8                                                                              4.8                                                                              4.8                                                                              4.8                                                                              4.8                                                                              4.8                                                                              4.8                                          PEG*.sup.4     1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                                                                              1.5                                          cryst. silicate (1)*.sup.5                                                                   2.5                                                                              5  7.5                                                      cryst. sodium aluminosilicate                                                                20 20 20 25 20 20 20                                           (zeolite 4A)                                                                  tetrasodium    2.5                                                                              2.5                                                                              2.5   5                                                  N,N-bis(carboxymethyl)-                                                       glutamate                                                                     polyacrylic acid              5                                               (Mw = 8,000)                                                                  acrylic acid-maleic acid copolymer                                                           2.5                                                                              2.5                                                                              2.5         5                                            (Mw = 50,000)                                                                 enzyme*.sup.6  1.8                                                                              1.8                                                                              1.8                                                                              1.8                                                                              1.8                                                                              1.8                                                                              1.8                                          fluorescent dye*.sup.7                                                                       0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                                                              0.5                                          perfume        0.4                                                                              0.4                                                                              0.4                                                                              0.4                                                                              0.4                                                                              0.4                                                                              0.4                                          water          6  6  6  6  6  6  6                                        detergency against sebum dirt (%)                                                                64.8                                                                             65.6                                                                             66.7                                                                             51.8                                                                             58.5                                                                             60.2                                                                             61.4                                     detergency against mud dirt (%)                                                                  58.8                                                                             59.0                                                                             60.1                                                                             48.6                                                                             49.7                                                                             57.3                                                                             55.6                                     __________________________________________________________________________     (Notes)                                                                       *.sup.1 sodium salt of linear alkyl(C.sub.12 --C.sub.13)benzenesulfonic       acid                                                                          *.sup.2 sodium alkyl(C.sub.12 --C.sub.18) sulfate                             *.sup.3 polyoxyethylene(average number of ethylene oxide molecules added:     8) alkyl(C.sub.12 --C.sub.14) ether                                           *.sup.4 average molecular weight: 8,000                                       *.sup.5 SKS6 (a product of Hoechst Tokuyama Ltd., average particle            diameter: 30 μm, phase layer sodium silicate of Na.sub.2 O.2.0             SiO.sub.2, ion exchange capacity of Na.sub.2 O.2SiO.sub.2 : 220 CaCO.sub.     mg/g, pH of 0.1% dispersion: higher than 11)                                  *.sup.6 a 2:1:1:1 mixture of Sabinase 12.0TW (a product of Novo Nordisk       Industry), Lipolase 100T (a product of Novo Nordisk Industry), Ceiluzyme      0.1T (a product of Novo Nordisk Industry), and Termamyl 60T (a product of     Novo Nordisk Industry)                                                        *.sup.7 a 1:1 mixture of Cinopal CBSX (a product of CibaGeigy Corporation     and Cinopal DMSX                                                         

We claim:
 1. A detergent composition comprising(a) 15 to 50% by weightof an anionic surfactant, (b) a polymer comprising units derived from atleast one member selected from the group consisting of monoethylenicallyunsaturated monocarboxylic acids and monoethylenically unsaturateddicarboxylic acids and having a weight-average molecular weight of 1,000to 150,000, or a salt of the polymer, (c) anN,N-bis(carboxymethyl)glutamic acid salt represented by the followingformula (I): ##STR5## wherein M is a hydrogen atom, an alkali metal, analkaline earth metal, an ammonium or a basic amino group, provided thata plurality of M's may be the same as or different from each other, and(d) 5 to 40% by weight of a crystalline aluminosilicate,the total amountof the components (b) and (c) being 1 to 20% by weight based on thecomposition, the weight ratio of the component (b) to the component (c)ranging from 1/10 to 10/1.
 2. The composition according to claim 1,which comprises(a) 25 to 45% by weight of an anionic surfactant, (b) apolymer comprising units derived from at least one member selected fromthe group consisting of monoethylenically unsaturated monocarboxylicacids and monoethylenically unsaturated dicarboxylic acids and having aweight-average molecular weight of 10,000 to 100,000, or a salt of thepolymer, (c) an N,N-bis(carboxymethyl)glutamic acid salt represented bythe formula (I) as defined in claim 1, and (d) 10 to 35% by weight of acrystalline aluminosilicate,the total amount of the components (b) and(c) being 1 to 10% by weight based on the composition, the weight ratioof the component (b) to the component (c) ranging from 3/10 to 10/3. 3.The composition according to claim 1, wherein the component (b)comprises repeating units represented by the following formula (IV):##STR6## wherein M is a counter ion and a copolymerizing ratio of x/yranges from 0/10 to 5/5 as a mole ratio.
 4. The composition according toclaim 1, which further contains a crystalline silicate.
 5. Thecomposition according to claim 1, which further contains a nonionicsurfactant, an amphoteric surfactant, a cationic surfactant, a builderor an enzyme.
 6. The composition according to claim 1, wherein in theformula (I) for the component (c) M is sodium.